Hot-melt adhesive compositions including vulcanized styrene block copolymers

Abstract

A hot-melt adhesive includes a dynamically vulcanized composition comprising the reaction product of a thermoplastic elastomer, a polyolefin polymer, oil, a tackifier, and a silane compound. In aspects disclosed herein, the thermoplastic elastomer comprises a cross-linkable polymer composition including (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene terpolymer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and EPDM. The hot-melt adhesive is extrudable as a thin film and exhibits hot water resistance, making it particularly suitable for garment and textile seam applications.

Description

HOT-MELT ADHESIVE COMPOSITIONS INCLUDING VULCANIZED STYRENEBLOCK COPOLYMERSCLAIM OF PRIORITY

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 596,083 bearing Attorney Docket Number 1202322 and filed on November 3, 2023, which is hereby incorporated by reference in its entirety.TECHNICAL FIELD

[0002] Embodiments of the present disclosure are generally related to dynamically vulcanizable compositions and hot-melt adhesives including the same.BACKGROUND

[0003] Hot-melt adhesives can be used as a solvent-free method for bonding solid or flexible substrates, such as textiles. Such hot-melt adhesives are typically prepared using film extrusion processes. To enable the use of film extrusion processes, conventional hot-melt adhesives employ low molecular weight polymers. However, the low molecular weight polymers can lack high temperature performance, rendering them unsuitable for hot water washing. On the other hand, high molecular weight polymers exhibit improved high temperature resistance, but are not suitable for thin film extrusion.

[0004] Accordingly, there is a need for alternative hot-melt adhesives that are suitable for thin film extrusion while exhibiting good high temperature performance, bonding, and washing resistance.SUMMARY

[0005] In light of the disclosure herein, and without limiting the scope of the invention in any way, in a first aspect of the present disclosure, which may be combined with any other aspect listed herein unless specified otherwise, a hot-melt adhesive includes a dynamically vulcanized composition comprising the reaction product of a cross-linkable thermoplastic elastomer composition, a polyolefin polymer, oil, a tackifier, and a silane compound. In aspects of thedisclosure, the cross-linkable polymer composition includes (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene terpolymer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and EPDM.

[0006] In a second aspect, which may be combined with any other aspect listed herein unless specified otherwise, a hot-melt adhesive includes a partially unsaturated conjugated diene-vinyl aromatic copolymer selected from the group consisting of partially hydrogenated styrenebutadiene rubber, partially hydrogenated styrene-butadiene block copolymers, partially hydrogenated styrene-isoprene block copolymers, partially hydrogenated styrene-butadiene- isoprene rubber, partially hydrogenated styrene-butadiene / isoprene block copolymers, partially hydrogenated styrene-butadiene-isoprene block copolymers, and combinations thereof.

[0007] In a third aspect, a hot-melt adhesive includes the hot-melt adhesive of any other aspect listed herein unless specified otherwise, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer a block copolymer that includes a block defined by formula (I):wherein the w, x, y, and z units are randomly distributed in the block, each Ri is independently a hydrogen atom or a methyl group, each R2 is independently a hydrogen atom or a methyl group with the proviso that at least one R2 per unit is a hydrogen atom; and the molar percent of the sum of the y and z units out of the total sum of the w, x, y, and z units in the block is from about 30% to about 90%.

[0008] In a fourth aspect, a hot-melt adhesive includes the hot-melt adhesive of any other aspect listed herein unless specified otherwise, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer has a number average molecular weight from about 50,000 g / mol to about 200,000 g / mol.

[0009] In a fifth aspect, a hot-melt adhesive includes the hot-melt adhesive of any other aspect listed herein unless specified otherwise, wherein the fully hydrogenated conjugated diene-vinyl aromatic copolymer has a number average molecular weight from about 50,000 g / mol to about 200,000 g / mol.

[0010] In a sixth aspect, a hot-melt adhesive webbing comprises the hot-melt adhesive of any other aspect listed herein unless specified otherwise.

[0011] In a seventh aspect, a hot-melt adhesive film comprises the hot-melt adhesive of any of the first through fourth aspects. In some aspects, the adhesive film has a thickness of 20 pm to 300 pm. In some aspects, the adhesive film is part of a multilayer composite comprising two or more films. According to some aspects, the adhesive film is part of a multilayer composite comprising the film adhered to a fabric backing. In any of the aspects, wherein the adhesive film is part of a multilayer composite comprising the film adhered to a release liner. In some aspects, the adhesive film has a width of 5 cm to 40 cm.

[0012] In an eighth aspect, a seam comprises a first section of fabric, a second section of fabric at least partially overlapping the first section of fabric to form a seam section, and a hot-melt adhesive layer in the seam section adhering the first section of fabric to the second section of fabric, wherein the adhesive layer comprises an adhesive film or an adhesive webbing comprising the hot-melt adhesive composition of any other aspect listed herein unless specified otherwise. According to some aspects, the seam section includes stitches attaching the first section of fabric to the second section of fabric. According to other aspects, wherein the seam section is a stitchless seam section. In any of the aspects, the first section of fabric and the second section of fabric each comprise nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, elastane, or a combination thereof. In any of the aspects disclosed herein, the adhesive layer is the adhesive film or the adhesive webbing.

[0013] In a ninth aspect, a method of preparing a seam comprises supplying a first section of fabric, a second section of fabric, and a hot-melt adhesive layer, situating the hot-melt adhesive layer between the first section of fabric and the second section of fabric to form a seam section, wherein the second section of fabric at least partially overlaps the first section of fabric, and heatingthe seam section such that the adhesive layer adheres the first section of fabric and the second section of fabric. In any of the aspects described herein, the hot-melt adhesive layer compromises an adhesive composition of any other aspect described herein unless specified otherwise.DETAILED DESCRIPTION

[0014] Disclosed herein are hot-melt adhesive compositions, and more specifically, hot-melt adhesive compositions comprising a dynamically vulcanized composition comprising the reaction product of a thermoplastic elastomer, a polyolefin polymer, oil, a tackifier, and a silane compound. In aspects of the disclosure, the thermoplastic elastomer comprises a cross-linkable polymer composition including (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and, optionally, ethylene propylene diene terpolymer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and EPDM. The hot-melt adhesive compositions exhibit good high temperature performance, bonding, and washing resistance, while being suitable for thin film extrusion.

[0015] The terminology as set forth herein is for description of the aspects only and should not be construed as limiting the disclosure as a whole. All references to singular characteristics or limitations of the present disclosure shall include the corresponding plural characteristic or limitation, and vice versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made. Unless otherwise specified, “a,” “an,” “the,” and “at least one” are used interchangeably. Furthermore, as used in the description and the appended claims, the singular forms “a,” “an,” and “the” are inclusive of their plural forms, unless the context clearly indicates otherwise.

[0016] To the extent that the term “includes” or “including” is used in the description or the claims, it is intended to be inclusive in a manner similar to the term “comprising” as that term is interpreted when employed as a transitional word in a claim. Furthermore, to the extent that the term “or” is employed (e.g., A or B) it is intended to mean “A or B or both.” When the applicants intend to indicate “only A or B but not both” then the term “only A or B but not both” will be employed. Thus, use of the term “or” herein is the inclusive, and not the exclusive use.

[0017] The hot-melt adhesives of the present disclosure can comprise, consist of, or consist essentially of the essential elements of the disclosure as described herein, as well as any additional or optional element described herein, or which is otherwise useful in hot-melt adhesive applications.

[0018] All percentages, parts, and ratios as used herein are by weight of the total blend on an “dry” basis, i.e., without solvents, unless otherwise specified.

[0019] All ranges and parameters, including but not limited to percentages, parts, and ratios, disclosed herein are understood to encompass any and all sub-ranges assumed and subsumed therein, and every number between the endpoints. For example, a stated range of “1 to 10” should be considered to include any and all sub-ranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less (e.g., 1 to 6.1, or 2.3 to 9.4), and to each integer (1, 2, 3, 4, 5, 6, 7, 8, 9, and 10) contained within the range. Ranges may be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another embodiments includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by the use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0020] The term “wt.%,” as described herein, refers to the weight fraction of the individual component based on a total weight of the dynamically vulcanized composition, unless otherwise noted.

[0021] The term “number average molecular weight,” as described herein, refers to a total weight of polymer divided by the total number of molecules as measured using gel permeation chromatography (GPC) and polystyrene standards.

[0022] The term “melt flow rate,” as described herein, refers to the ability of a material’s melt to flow under pressure as measured according to ASTM DI 238 at the given temperature and given weight.

[0023] The term “density,” as described herein, refers to the mass per unit volume of a material as measured according to ASTM D792 at 23 °C.

[0024] The term “specific gravity,” as described herein, refers to the ratio of the density of a material to the density of water as measured according to ASTM D792 at 23 °C.

[0025] The term “Mooney viscosity,” as described herein, refers to the viscosity reached after a rotor rotates for a given time interval at the specified temperature as measured according to ASTM D1646.

[0026] The term “yield,” as described herein, refers to the point on a stress-strain curve that indicates the limit of elastic behavior and the beginning of plastic behavior.

[0027] The term “tensile strength at yield,” as described herein, refers to the maximum stress that a material can withstand while being stretched before it begins to change shape permanently as measured according to ASTM D638 at 23 °C and a rate of strain of 0.85 mm / s.

[0028] The term “tensile elongation at yield,” as described herein, refers to the ratio between the increased length and initial length at the yield point as measured according to ASTM D638 at 23 °C and a rate of strain of 0.85 mm / s.

[0029] The term “tensile strength at break,” as described herein, refers to the maximum stress that a material can withstand while stretching before breaking as measured according to ASTM D638 at 23 °C and a rate of strain of 0.85 mm / s.

[0030] The term “tensile elongation at break,” as described herein, refers to the ratio between increased length and initial length after breakage as measured according to ASTM D638 at 23 °C and a rate of strain at 0.85 mm / s.

[0031] The term “Shore A hardness,” as described herein, refers to the hardness of a material as measured according to ASTM D2240.

[0032] The phrase “Dynamic Mechanical Analysis (DMA) storage modulus,” as described herein, refers to a technique that is used to determine storage modulus (MPa) as a function of temperature at a certain frequency.

[0033] The phrase “fabric bonding peel force,” as described herein, refers to the measurement of the properties of an adhesive bond (average force per width of a substrate (lbs / in)), and involves applying a tensile force to a flexible substrate that is bound by an adhesive to another flexible substrate.

[0034] The term “polyolefin,” as described herein, refers to a polymer that has a crystalline and amorphous phase prepared from olefin monomers.

[0035] The term “polyolefin elastomer (POE),” as described herein, refers to a low crystalline (i.e., less than or equal to 25% crystalline) polymer prepared from olefin monomers.

[0036] The term “silane grafted,” as described herein, refers to the thermoplastic elastomer having a silane side chain connected to the polymer main chain.

[0037] The term “copolymer,” as described herein, refers to a polymer formed when two or more different monomers are polymerized to form a chain.

[0038] The term “block,” as described herein, refers to a portion of a polymer, comprising many constitutional units, that has at least one feature which is not present in the adjacent portions.

[0039] As discussed above, hot-melt adhesives may have good bonding and other characteristics that enable them to be prepared using thin film extrusion processes, but may lack high temperature resistance required by certain applications, including, for example, garment and textile bonding applications. In such applications, the lack of high temperature resistance may lead to a break down of the adhesive when the garments or textiles are washed in hot water.

[0040] The present inventive concepts are directed to a hot-melt adhesive composition including a dynamically vulcanized composition comprising the reaction product of a thermoplastic elastomer, a polyolefin polymer, an oil, a tackifier, and a silane compound. By dynamicallyvulcanized, it is meant that a thermoplastic material and an elastomer are cross-linked under dynamic conditions. The thermoplastic elastomer comprises a cross-linkable polymer composition that includes (i) a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene terpolymer (EPDM); or (ii) a fully hydrogenated conjugated diene-vinyl aromatic copolymer and EPDM. The hot-melt adhesive can be extruded as a thin film and exhibits good high temperature resistance. Additionally, the hot-melt adhesive is moisture curable without the use of a catalyst, which can extend the shelflife of the hot-melt adhesive.

[0041] Disclosed herein are dynamically vulcanizable compositions having an advantageous temperature resistance (e.g., an increased peel force following immersion in 80 °C water for 24 hours), while having good thin film extrusion at a particular thickness, such as, for example, a thickness of 1-3 mil. The vulcanization package including an organic peroxide and a silane can enable carbon-carbon bond crosslinking of the thermoplastic elastomer and polyolefin polymer upon blending without the need for additional steps or materials, such as a moisture cure catalyst.

[0042] Conventional processes for forming hot-melt adhesives include a thin film extrusion process. Although polymers such as styrene-ethylene-butylene-styrene (SEBS) work well in hot- melt adhesives for room temperature and low temperature washing, the low molecular weight of the SEBS that makes it suitable for thin film extrusion also renders it unsuitable for high temperature environments, such as washing at temperatures of 80 °C or above. The use of a high molecular weight SEBS may provide improved high temperature resistance, but is generally incompatible with thin film extrusion. The hot-melt adhesive composition of the present disclosure addresses these issues by providing a hot-melt adhesive that is cross-linked to provide high temperature performance while remaining processable by thin film extrusion methods. The thermoplastic elastomer of the present disclosure can be blended with a silane crosslinking composition directly in the conventional conversion process, thus eliminating the initial silane grafting step. The crosslinking of the thermoplastic elastomer is performed in a one-step process where a hot-melt adhesive film is formed by extrusion. In addition, the hot-melt adhesive composition is moisture curable without the use of a catalyst, which can extend the shelf life of the product.Thermoplastic Elastomer

[0043] The thermoplastic elastomer of the hot-melt adhesive composition comprises at least one cross-linkable polymer composition comprising vinyl aromatic monomeric units and conjugated diene monomeric units. The conjugated diene monomeric units can be selected from the group consisting of 1,3-butadiene monomeric units, 2, 3 -dimethyl- 1,3 -butadiene, piperylene monomeric units, isoprene monomeric units, and combinations thereof. The vinyl aromatic monomeric units can be selected from the group consisting of styrene monomeric units, a-methyl styrene monomeric units, p-methyl styrene monomeric units, o-m ethyl styrene monomeric units, p- butylstyrene monomeric units, p-tertbutylstyrene monomeric units, and combinations thereof.

[0044] In any of the exemplary aspects, the cross-linkable polymer composition may comprise a conjugated diene-vinyl aromatic copolymer from the group consisting of partially saturated or fully hydrogenated conjugated diene-vinyl aromatic copolymers. In any of the exemplary aspects, the conjugated diene-vinyl aromatic copolymer is selected from the group consisting of styrene-butadiene rubber, styrene-butadiene block copolymers, styrene-isoprene block copolymers (SIS), styrene-butadiene-isoprene rubber, styrene-butadiene / isoprene block copolymers, styrene-butadiene-isoprene block copolymers, nitrile-butadiene rubber, and combinations thereof, which may be partially unsaturated (i.e., partially hydrogenated) or fully hydrogenated.

[0045] According to any of the exemplary aspects, the conjugated diene-vinyl aromatic copolymer may be a block copolymer that includes a block defined by formula (I):wherein the w, x, y, and z units are randomly distributed in block, each Ri is independently a hydrogen atom or a methyl group, and each R2 is independently a hydrogen atom or a methyl group with the proviso that at least one R2 per unit is a hydrogen atom.

[0046] In a polymer block defined by formula (I), the molar percent of the sum of the y and z units out of the total sum of the w, x, y, and z units in the block may be from about 30% to about 90%. The molar percent of the sum of the y and z units out of the total sum of the w, x, y, and z units in the block may be from about 50% to about 70%. The molar percent of the sum of the y and z units out of the total sum of the w, x, y, and z units in the block may be greater than or equal to about 30%, greater than or equal to about 35%, greater than or equal to about 40%, greater than or equal to about 45%, or even greater than or equal to about 50%. The molar percent of the sum of the y and z units out of the total sum of the w, x, y, and z units in the block may be less than or equal to about 90%, less than or equal to about 85%, less than or equal to about 80%, less than or equal to about 75%, or even less than or equal to about 70%. The molar percent of the sum of the y and z units out of the total sum of the w, x, y, and z units in the block may be from about 30% to about 90%, from about 30% to about 85%, from about 30% to about 80%, from about 30% to about 75%, from about 30% to about 70%, from about 35% to about 90%, from about 35% to about 85%, from about 35% to about 80%, from about 35% to about 75%, from about 35% to about 70%, from about 40% to about 90%, from about 40% to about 85%, from about 40% to about 80%, from about 40% to about 75%, from about 40% to about 70%, from about 45% to about 90%, from about 45% to about 85%, from about 45% to about 80%, from about 45% to about 75%, from about 45% to about 70%, from about 50% to about 90%, from about 50% to about 85%, from about 50% to about 80%, from about 50% to about 75%, or from about 50% to about 70%, or any and all endpoints or subranges therebetween.

[0047] In a polymer block defined by formula (I), the ratio of y units to w units may be greater than the ratio of x units to z units. The ratio of y units to w units may also be less than the ratio of x units to z units.

[0048] In any or all of the aspects described herein, the conjugated diene-vinyl aromatic copolymer may be a block copolymer that includes a block defined by formula (II):wherein the a, b, c, and d units are randomly distributed in the block.

[0049] In a polymer block defined by formula (II), the molar percent of the sum of the c units and d units out of the total sum of the a, b, c, and d units in the block may be from about 30% to about 90%. The molar percent of the sum of the c units and d units out of the total sum of the a, b, c, and d units in the block may be from about 50% to about 70%. The molar percent of the sum of the c units and d units out of the total sum of the a, b, c, and d units in the block may be greater than or equal to about 30%, greater than or equal to about 35%, greater than or equal to about 40%, greater than or equal to about 45%, or even greater than or equal to about 50%. The molar percent of the sum of the c units and d units out of the total sum of the a, b, c, and d units in the block may be less than or equal to about 90%, less than or equal to about 85%, less than or equal to about 80%, less than or equal to about 75%, or even less than or equal to about 70%. The molar percent of the sum of the c units and d units out of the total sum of the a, b, c, and d units in the block may be from about 30% to about 90%, from about 30% to about 85%, from about 30% to about 80%, from about 30% to about 75%, from about 30% to about 70%, from about 35% to about 90%, from about 35% to about 85%, from about 35% to about 80%, from about 35% to about 75%, from about 35% to about 70%, from about 40% to about 90%, from about 40% to about 85%, from about 40% to about 80%, from about 40% to about 75%, from about 40% to about 70%, from about 45% to about 90%, from about 45% to about 85%, from about 45% to about 80%, from about 45% to about 75%, from about 45% to about 70%, from about 50% to about 90%, from about 50% to about 85%, from about 50% to about 80%, from about 50% to about 75%, or from about 50% to about 70%, or any and all endpoints and subranges therebetween.

[0050] In a polymer block defined by formula (II), the ratio of c units to a units may be greater than the ratio of d units to b units. The ratio of c units to a units may also be less than the ratio of d units to b units.

[0051] In accordance with various aspects, the conjugated diene-vinyl aromatic copolymer can be a triblock copolymer that includes two polystyrene end blocks. The styrene content of the two polystyrene end blocks in the conjugated diene-vinyl aromatic copolymer may be from about 10 wt.% to about 50 wt.%. The styrene content of the two polystyrene end blocks in the conjugated diene-vinyl aromatic copolymer may be greater than or equal to about 10 wt.%, greater than or equal to about 15 wt.%, greater than or equal to about 20 wt.%, greater than or equal to about 25 wt.%, or even greater than or equal to about 27 wt.%. The styrene content of the two polystyrene end blocks in the conjugated diene-vinyl aromatic copolymer may be less than or equal to about 50 wt.%, less than or equal to about 45 wt.%, less than or equal to about 40 wt.%, less than or equal to about 35 wt.%, or even less than or equal to about 33 wt.%. The styrene content of the two polystyrene end blocks in the conjugated diene-vinyl aromatic copolymer may be from about 10 wt.% to about 50 wt.%, from about 10 wt.% to about 45 wt.%, from about 10 wt.% to about 40 wt.%, from about 10 wt.% to about 35 wt.%, from about 10 wt.% to about 33 wt.%, from about 15 wt.% to about 50 wt.%, from about 15 wt.% to about 45 wt.%, from about 15 wt.% to about 40 wt.%, from about 15 wt.% to about 35 wt.%, from about 15 wt.% to about 33 wt.%, from about 20 wt.% to about 50 wt.%, from about 20 wt.% to about 45 wt.%, from about 20 wt.% to about 40 wt.%, from about 20 wt.% to about 35 wt.%, from about 20 wt.% to about 33 wt.%, from about 25 wt.% to about 50 wt.%, from about 25 wt.% to about 45 wt.%, from about 25 wt.% to about 40 wt.%, from about 25 wt.% to about 35 wt.%, from about 25 wt.% to about 33 wt.%, from about 27 wt.% to about 50 wt.%, from about 27 wt.% to about 45 wt.%, from about 27 wt.% to about 40 wt.%, from about 27 wt.% to about 35 wt.%, or from about 27 wt.% to about 33 wt.%, or any and all endpoints and subranges therebetween.

[0052] In any or all of the aspects described herein, the conjugated diene-vinyl aromatic copolymer may have a number average molecular weight of from about 30,000 g / mol to about 400,000 g / mol. For example, the conjugated diene-vinyl aromatic copolymer may have a number average molecular weight of greater than or equal to 30,000 g / mol, greater than or equal to about50,000 g / mol, greater than or equal to about 100,000 g / mol, or even greater than or equal to about 150,000 g / mol. The conjugated diene-vinyl aromatic copolymer may additionally or alternatively have a number average molecular weight less than or equal to about 400,000 g / mol, less than or equal to about 350,000 g / mol, less than or equal to about 300,000 g / mol, or even less than or equal to about 250,000 g / mol. According to one or more aspects described herein, the conjugated diene- vinyl aromatic copolymer may have a number average molecular weight of from about 30,000 g / mol to about 400,000 g / mol, from about 30,000 g / mol to about 350,000 g / mol, from about 30,000 g / mol to about 300,000 g / mol, from about 30,000 g / mol to about 250,000 g / mol, from about 50,000 g / mol to about 400,000 g / mol, from about 50,000 g / mol to about 350,000 g / mol, from about 50,000 g / mol to about 300,000 g / mol, from about 50,000 g / mol to about 250,000 g / mol, from about 50,000 g / mol to about 200,000 g / mol, from about 100,000 g / mol to about 400,000 g / mol, from about 100,000 g / mol to about 350,000 g / mol, from about 100,000 g / mol to about 300,000 g / mol, from about 100,000 g / mol to about 250,000 g / mol, from about 150,000 g / mol to about 400,000 g / mol, from about 150,000 g / mol to about 350,000 g / mol, from about 150,000 g / mol to about 300,000 g / mol, or even from about 150,000 g / mol to about 250,000 g / mol, or any and all endpoints and subranges therebetween.

[0053] In accordance with the present disclosure, when the thermoplastic elastomer has carbon-carbon double bond sites, the carbon-carbon double bond may be partially hydrogenated. Without being bound by theory, it is believed that crosslinking of partially hydrogenated conjugated diene-vinyl aromatic copolymer occurs at least in part at the non-hydrogenated sites (i.e., carbon-carbon double bonds such as those located on the conjugated diene residues) and the amount of reactive sites may be set by tailoring the hydrogenation of the conjugated diene-vinyl aromatic copolymer. By controlling the level of hydrogenation, the amount of crosslinking may also be controlled. Reducing the degree of hydrogenation of the conjugated diene-vinyl aromatic copolymer may improve the cross-link density and heat resistance of the resulting partially crosslinked polymer system. In accordance with the present disclosure, the conjugated diene-vinyl aromatic copolymer may have a degree of hydrogenation greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%o, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 90%, or even greater than or equal to about 95%, based on the molar ratio of the hydrogenated carbon-carbon doublebonds to the total carbon-carbon double bonds in the pre-partially hydrogenated conjugated diene- vinyl aromatic copolymer. In any of the exemplary aspects, the conjugated diene-vinyl aromatic copolymer may have a degree of hydrogenation in the range of about 30% to about 99%, or about 35% to about 95%, or about 40% to about 90%, or about 45% to about 85%, or about 50% to about 80%, or about 55% to about 75%, based on the unsaturated groups of the conjugated diene monomeric units in the pre-partially hydrogenated conjugated diene-vinyl aromatic copolymer.

[0054] In accordance with the various aspects, the conjugated diene-vinyl aromatic copolymer may be a partially hydrogenated having a hard phase and a soft phase, the general configuration being:A— B,A— B — A, orA— B— A', wherein prior to hydrogenation, each A and A' blocks is a hard phase comprised of vinyl aromatic monomeric units and each B block is a soft phase comprised of conjugated diene monomeric units. “Hard phase” refers to a portion of the block copolymer having a glass transition temperature from 90 °C to 120 °C. “Soft phase” refers to a portion of the block copolymer having a glass transition less than -20 °C.

[0055] In various aspects, the conjugated diene-vinyl aromatic copolymer is included in the hot-melt adhesive composition in an amount of from about 20 wt.% to about 95 wt.%, based on a total weight of the hot-melt adhesive composition. For example, the hot-melt adhesive composition may include the conjugated diene-vinyl aromatic copolymer in an amount of from about 25 wt.% to about 90 wt.%, such as from about 30 wt.% to about 85 wt.%, from about 32 wt.% to about 80 wt.%, from about 35 wt.% to about 75 wt.%, from about 37 wt.% to about 70 wt.%, or from about 40 wt.% to about 65 wt.%, based on a total weight of the hot-melt adhesive composition, including any and all endpoints and subranges therebetween. In any of the aspects disclosed herein, the hot-melt adhesive composition may include the conjugated diene-vinyl aromatic copolymer in an amount of from about 20 wt.% to about 60 wt.%, including, for example,from about 23 wt.% to about 55 wt.%, from about 25 wt.% to about 50 wt.%, about 27 wt.% to about 47 wt.%, or from about 30 wt.% to about 45 wt.%, based on a total weight of the hot-melt adhesive composition, including any and all endpoints and subranges therebetween.

[0056] Examples of suitable conjugated diene-vinyl aromatic copolymers that are commercially available include G1654 and G1650 (styrene-ethylene-butylene-styrene (SEBS) triblock copolymers having a molecular weight around 200K and 100K, respectively) and p-SEBS (a partially hydrogenated SEBS with a molecular weight around 100K and including approximately 30% styrene end block and about 80% hydrogenation) under the brand name KRATON™, available from Kraton.

[0057] In any of the exemplary aspects, the cross-linkable polymer composition may further include at least one polymer comprising at least one cross-linkable functional group. Exemplary polymers having at least one cross-linkable functional group include ethylene-propylene-diene rubber (EPDM), pms-SEBS (styrene-ethylene-butylene-styrene), heat cured silicone rubber (HCR), ethyl ene-propylene rubber (EPR), butyl rubber, halobutyl rubber, halogenated rubbery copolymers of p-alkylstyrene and at least one isomonoolefm having 4 to 7 carbon atoms, nitrile rubber and its copolymers, styrene-acrylate-acrylonitrile rubber (Sunigum®), hydrogenated nitrile rubber, acrylate rubber and its copolymers, ethylene-acrylate-glycidyl methacrylate elastomer, polyamide elastomer, polyester elastomer, natural rubber, and a polyolefin copolymeric elastomer having at least two repeat units that are derived from the group consisting of ethylene, propylene, butene, hexene, and octene. For example, the polymer comprising at least one cross-linkable functional group can be an EPDM rubber with either norbornene, hexadiene or dicyclopentadiene monomer units.

[0058] Examples of suitable EPDM rubbers that are commercially available include extrusion grade NORDEL™ IP 4725P from The Dow Chemical Company.

[0059] In various aspects, the polymer comprising at least one cross-linkable functional group is included in the hot-melt adhesive composition in an amount of from about 0 wt.% to about 50 wt.%, based on a total weight of the hot-melt adhesive composition. For example, the hot-melt adhesive composition may include the polymer comprising at least one cross-linkable functionalgroup in an amount of from about 1 wt.% to about 40 wt.%, such as from about 3 wt.% to about 35 wt.%, from about 5 wt.% to about 30 wt.%, from about 8 wt.% to about 25 wt.%, from about 10 wt.% to about 20 wt.%, or from about 7 wt.% to about 22 wt.%, based on a total weight of the hot-melt adhesive composition, including any and all endpoints and subranges therebetween.

[0060] In any of the exemplary aspects, when the cross-linkable polymer composition comprises a fully hydrogenated conjugated diene-vinyl aromatic copolymer, at least one additional polymer comprising at least one cross-linkable functional group is included in the cross-linkable polymer composition. In any of the exemplary aspects, when the cross-linkable polymer composition comprises a partially unsaturated conjugated diene-vinyl aromatic copolymer, the cross-linkable polymer composition can optionally include at least one additional polymer comprising at least one cross-linkable functional group.Vulcanization Package

[0061] The vulcanization package of the dynamically vulcanizable composition comprises a silane crosslinker and an organic peroxide. As described herein, the vulcanization package facilitates peroxide vulcanization resulting in carbon-carbon bond crosslinking of the thermoplastic elastomer upon blending without the need for additional steps or materials. During blending of the hot-melt adhesive composition to form the cross-linked polymer system, the thermoplastic elastomer may be grafted with silane moieties. The blend may be aged such that the cross-linked polymer system forms silane cross-links from the silane-grafts.

[0062] The silane crosslinker of the vulcanization package may comprise various silanes. Examples of suitable silanes include the silane represented by the following formula:SiRxH4-x wherein x is 1-4, and each R is individually and independently a monovalent hydrocarbon group or a monovalent alkoxy group.

[0063] In various aspects, the monovalent hydrocarbon group may be a linear, cyclic, or branched group. The monovalent hydrocarbon group may have 1-12 carbon atoms, 2-10 carbonatoms, or 3-8 carbon atoms. The monovalent hydrocarbon group may include one or more carboncarbon double bonds. The monovalent hydrocarbon group may include one or more aromatic groups.

[0064] In accordance with the present disclosure, the monovalent alkoxy group may be a monovalent hydrocarbon group attached to an oxygen atom. The monovalent hydrocarbon group of the monovalent alkoxy group may be a linear, cyclic, or branched group. The monovalent hydrocarbon group of the monovalent alkoxy group may have 1-12 carbon atoms, 2-10 carbon atoms, or 3-8 carbon atoms. The monovalent hydrocarbon group of the monovalent alkoxy group may include one or more double carbon-carbon bonds. The monovalent hydrocarbon group of the monovalent alkoxy group may include one or more aromatic groups.

[0065] In any of the exemplary aspects, the silane crosslinker may comprise vinyl trialkoxysilane. For example, the silane crosslinker may comprise vinyl trimethoxysilane, vinyl triethoxysilane, or a combination thereof.

[0066] The silane crosslinker may have a specific gravity greater than or equal to about 0.90 or greater than or equal to about 0.95. The silane may have a specific gravity less than or equal to about 1.05 or less than or equal to about 1. The silane may have a specific gravity from about 0.90 to about 1.05, from about 0.90 to about 1.00, from about 0.95 to about 1.05, or from about 0.95 to about 1 .00, including any and all endpoints and subranges therebetween.

[0067] In any of the aspects disclosed herein, the silane crosslinker may have a boiling point greater than or equal to about 75 °C or greater than or equal to about 100 °C. The silane crosslinker may have a boiling point less than or equal to about 150 °C or less than or equal to about 125 °C. For example, the silane crosslinker may have a boiling point from about 75 °C to about 150 °C, from about 75 °C to about 125 °C, from about 100 °C to about 150 °C, or from about 100 °C to about 125 °C, including any and all endpoints and subranges therebetween.

[0068] In any of the aspects disclosed herein, the silane crosslinker may have a number average molecular weight greater than or equal to about 50 g / mol, greater than or equal to about 100 g / mol, greater than or equal to 150 g / mol, or greater than or equal to about 200 g / mol. Thesilane crosslinker may have a number average molecular weight less than or equal to about 500 g / mol, less than or equal to about 400 g / mol, or less than or equal to about 300 g / mol. The silane crosslinker may have a number average molecular weight from about 50 g / mol to about 500 g / mol, from about 50 g / mol to about 400 g / mol, from about 50 g / mol to about 300 g / mol, from about 100 g / mol to about 500 g / mol, from about 100 g / mol to about 400 g / mol, from about 100 g / mol to about 300 g / mol, from about 150 g / mol to about 500 g / mol, from about 150 g / mol to about 400 g / mol, from about 150 g / mol to about 300 g / mol, from about 200 g / mol to about 500 g / mol, from about 200 g / mol to about 400 g / mol, or from about 200 g / mol to about 300 g / mol, including any and all endpoints and subranges therebetween.

[0069] Examples of suitable silane crosslinkers that are commercially available include grade A-171 vinyltrimethoxy silane under SILQUEST™ brand from Momentive.

[0070] As mentioned above, the vulcanization package further includes an organic peroxide. The organic peroxide of the vulcanization package may comprise various peroxides and is not particularly limited. Examples of suitable peroxides include the peroxide represented by the following formula:R-O-O-R wherein each R is individually and independently a monovalent hydrocarbon group. In accordance with the present disclosure, the monovalent hydrocarbon group of the organic peroxide may be a linear, cyclic, or branched group. The monovalent hydrocarbon group of the organic peroxide may have 1-16 carbon atoms, 3-12 carbon atoms, or 5-10 carbon atoms. The monovalent hydrocarbon group of the organic peroxide may include one or more carbon-carbon double bonds. The monovalent hydrocarbon group of the organic peroxide may include one or more aromatic groups. In accordance with the present disclosure, the organic peroxide may comprise peroxyketal peroxide, di-tert alkyl peroxide, or a combination thereof. For example, the organic peroxide may comprise dicumyl peroxide (a di-tert alkyl peroxide).

[0071] In accordance with the present disclosure, the organic peroxide may have a density greater than or equal to about 1.00 g / cm3or greater than or equal to about 1.05 g / cm3. The organicperoxide may have a density less than or equal to about 1.20 g / cm3or less than or equal to about 1.15 g / cm3. The organic peroxide may have a density from about 1.00 g / cm3to about 1.20 g / cm3, from about 1.00 g / cm3to about 1.15 g / cm3, from about 1.05 g / cm3to about 1.20 g / cm3, or from about 1.05 g / cm3to about 1.15 g / cm3, including any and all endpoints and subranges therebetween.

[0072] Examples of suitable organic peroxide that are commercially available include grade BC-FF dicumyl peroxide under the PERK DOX® brand from AkzoNobel.

[0073] In accordance with the present disclosure, the weight ratio based on dry weight of the silane crosslinker and the organic peroxide in the vulcanization package may be 3: 1 or more, 4: 1 or more, or 5: 1 or more. The weight ratio based on dry weight of the silane crosslinker and the organic peroxide in the vulcanization package may be 20:1 or less, 15:1 or less, or 10: 1 or less. The weight ratio based on dry weight of the silane crosslinker and the organic peroxide in the vulcanization package may be from 3:1 to 20: 1, from 3:1 to 15: 1, from 3:1 to 10: 1, from 4:1 to 20: 1, from 4:1 to 15:1, from 4: 1 to 10: 1, from 5: 1 to 20:1, from 5: 1 to 15:1, from 5: 1 to 10: 1, including any and all endpoints and subranges therebetween. The dry weight of the silane crosslinker and the organic peroxide in the vulcanization package may be from 0.5 to 10% of the mass of the thermoplastic elastomer in the hot-melt adhesive, including from 1% to 8%, from 2 to 7%, and from 3 to 6%.

[0074] In any of the aspects disclosed herein, the vulcanization package may be in the form of a dry silane masterbatch comprising a carrier material loaded with the silane crosslinker and organic peroxide. The carrier material may comprise porous pellets, a filler material (e.g., silica, talc, calcium carbonate, microspheres, etc.), or a combination thereof. The porous pellets may comprise high porosity pellets, such as plastics selected from polypropylene, ethylene vinyl acetate, polyethylene, and mixtures thereof. The carrier material may be loaded by soaking the carrier material in a solution containing the silane crosslinker, the organic peroxide, and other components, if present (e.g., additives), and drying the carrier material to remove solvents in the solution. The silane / peroxide loading of the carrier material may be 20% or more, 30% or more, or 40% or more, based on the dry weight ratio of silane / peroxide to carrier. The silane / peroxide loading of the carrier material may be 80% or less, 70% or less, or 60% or less, based on the dry weight ratio of silane / peroxide to carrier. The silane / peroxide loading of the carrier material maybe from 20% to 80%, from 20% to 70%, from 20% to 60%, from 30% to 80%, from 30% to 70%, from 30% to 60%, from 40% to 80%, from 40% to 70%, from 40% to 60%, including any and all endpoints and subranges therebetween, based on the dry weight ratio of silane / peroxide to carrier. The dry silane masterbatch may be dry blended with the thermoplastic elastomer and fed to extrusion or injection molding processes for crosslinking the thermoplastic elastomer.

[0075] The vulcanization package may be present in the form of a solution, dispersion, or emulsion comprising the silane crosslinker and the organic peroxide. When forming the dry silane, the vulcanization package may be blended with the porous pellet to form the dry silane masterbatch, which may then be fed to an extrusion or injection molding process for crosslinking the thermoplastic elastomer. Alternatively, or in addition to the dry silane, the vulcanization package may be injected directly into the melt thermoplastic elastomer during extrusion or injection molding.

[0076] The hot-melt adhesive may comprise from about 0.5 wt.% to about 5 wt.% of the silane. In any of the exemplary aspects, the amount of silane in the hot-melt adhesive composition may be greater than or equal to about 0.5 wt.%, including, for example, at least 0.75 wt.%, at least 0.9 wt.%, at least 1 wt.%, at least 1.25 wt.%, at least 1.5 wt.%, at least 1.75 wt.%, or at least 2 wt.%, including all the endpoints and subranges therebetween. In any of the exemplary aspects, the amount of silane in the hot-melt adhesive composition may be less than or equal to about 5 wt.%, including, for example, less than or equal to about 4.75 wt.%, less than or equal to 4.5 wt.%, less than or equal to 4.2 wt.%, less than or equal to 4 wt.%, less than or equal to 3.7 wt.%, less than or equal to 3.5 wt.%, less than or equal to 3.2 wt.%, or less than or equal to about 3 wt. %, including all endpoints and subranges therebetween. The amount of silane in the hot-melt adhesive composition may be from 0.5 wt.% to 5 wt.%, including, for example, from 0.5 wt.% to about 4 wt.%, from about 0.5 wt.% to about 3 wt.%, from about 1 wt.% to about 5 wt.%, from about 1 wt.% to about 4 wt.%, or from about 1 wt.% to about 3 wt.%, including any endpoints and subranges therebetween.

[0077] While not wishing to be bound by theory, it is believed that increasing the organic peroxide amount in the dynamically vulcanizable composition improves the cross-link density and heat resistance of the resulting cross-linked polymeric composition. In any of the aspects disclosedherein, the hot-melt adhesive composition may comprise from about 0.05 wt.% to about 1 wt.% of the organic peroxide. The amount of organic peroxide in the hot-melt adhesive composition may be greater than or equal to about 0.05 wt.%, greater than or equal to about 0.1 wt.%, or even greater than or equal to about 0.2 wt.%. The amount of organic peroxide in the hot-melt adhesive composition may be less than or equal to about 1 wt.%, less than or equal to about 0.8 wt.%, less than or equal to about 0.6 wt.%, or even less than or equal to about 0.4 wt.%. The amount of organic peroxide in the hot-melt adhesive composition may be from about 0.05 wt.% to about 1 wt.%, from about 0.05 wt.% to about 0.8 wt.%, from about 0.05 wt.% to about 0.6 wt.%, from about 0.05 wt.% to about 0.4 wt.%, from about 0.1 wt.% to about 1 wt.%, from about 0.1 wt.% to about 0.8 wt.%, from about 0.1 wt.% to about 0.6 wt.%, from about 0.1 wt.% to about 0.4 wt.%, from about 0.2 wt.% to about 1 wt.%, from about 0.2 wt.% to about 0.8 wt.%, from about 0.2 wt.% to about 0.6 wt.%, or from about 0.2 wt.% to about 0.4 wt.%, including all endpoints and subranges therebetween.Olefin Polymer

[0078] The hot-melt adhesive composition further comprises an olefin polymer to tailor hardness and mechanical properties and improve flow properties. The olefin polymer may comprise polyolefin, polyolefin elastomer, or a combination thereof. For example, suitable examples of polyolefin include polypropylene, polyethylene, or a combination thereof. The polyolefin may be at least one of high-density polyethylene (e.g., greater than or equal to 0.940 g / cm3) or a crystalline polypropylene with a percent crystallinity of at least about 60%.

[0079] In accordance with the present disclosure, the olefin polymer may comprise polypropylene. The polypropylene may comprise a polypropylene homopolymer (i.e., composed of propylene monomers) or a polypropylene copolymer having greater than 50 wt.% propylene monomer and one or more additional comonomer such as C2 and C4-C12 alpha olefins. The polyethylene may comprise a polyethylene homopolymer (i.e., composed of ethylene monomers) or a polyethylene copolymer having greater than 50 wt % ethylene monomer and an additional comonomer, such as C3-C12 alpha olefins.

[0080] The polypropylene may have a melt flow rate (230 °C / 2.16 kg) greater than or equal to about 0.1 g / 10 min, greater than or equal to about 0.5 g / 10 min, greater than or equal to about 1 g / 10 min, or even greater than or equal to about 3 g / 10 min. The polypropylene may have a melt flow rate (230 °C / 2.16 kg) less than or equal to about 10 g / 10 min or even less than or equal to about 5 g / 10 min. The polypropylene may have a melt flow rate (230 °C / 2.16 kg) from about 0.1 g / 10 min to about 10 g / 10 min, from about 0.1 g / 10 min to about 5 g / 10 min, from about 0.5 g / 10 min to about 10 g / 10 min, from about 0.5 g / 10 min to about 5 g / 10 min, from about 1 g / 10 min to about 10 g / 10 min, from about 1 g / 10 min to about 5 g / 10 min, from about 3 g / 10 min to about 10 g / 10 min, or from about 3 g / 10 min to about 5 g / 10 min, or any and all subranges formed from any of these endpoints.

[0081] In accordance with the present disclosure, the polyolefin may have a density greater than or equal to about 0.80 g / cm3or even greater than or equal to about 0.85 g / cm3. The polyolefin may have a density less than or equal to about 1.10 g / cm3or even less than or equal to about 1.00 g / cm3. The polyolefin may comprise a density from about 0.80 g / cm3to about 1.10 g / cm3, from about 0.80 g / cm3to about 1.00 g / cm3, from about 0.85 g / cm3to about 1.10 g / cm3, or from about 0.85 g / cm3to about 1.00 g / cm3, or any and all subranges formed from any of these endpoints.

[0082] In accordance with the present disclosure, the polyolefin may have a melting point greater than or equal to about 100 °C, greater than or equal to about 110 °C, or even greater than or equal to about 120 °C.

[0083] In accordance with the present disclosure, the polyolefin may have a tensile strength at yield greater than or equal to about 25 MPa or even greater than or equal to about 30 MPa. The polyolefin may have a tensile strength at yield less than or equal to about 45 MPa or even less than or equal to about 40 MPa. The polyolefin may have a tensile strength at yield from about 25 MPa to about 45 MPa, from about 25 MPa, to about 40 MPa, from about 30 MPa to about 45 MPa, or from about 30 MPa to about 40 MPa, including any and all endpoints and subranges therebetween.

[0084] In accordance with the present disclosure, the polyolefin may have a tensile elongation at yield greater than or equal to about 3% or even greater than or equal to about 5%. The polyolefin may have a tensile elongation at yield less than or equal to about 20% or even lessthan or equal to about 15%. The polyolefin may have a tensile elongation at yield from about 3% to about 20%, from about 3% to about 15%, from about 5% to about 20%, or from about 5% to about 15%, including any and all endpoints and subranges therebetween.

[0085] Examples of suitable polyolefins that are commercially available include polypropylene homopolymer grade 1102KR under the FORMOLENE® brand from Formosa Plastics.

[0086] In accordance with the present disclosure, the polyolefin elastomer may comprise polypropylene elastomer. Examples of suitable polyolefin elastomers that are commercially available include polypropylene elastomer grades 6201 and 6202 under the VISTAMAXX™ brand from Exxon.

[0087] In accordance with the present disclosure, the polyolefin elastomer may comprise olefin block copolymer, ethylene alpha-olefin copolymer, or a combination thereof. The olefin block copolymer may comprise an ethylene alpha-olefin repeating unit. The ethylene alpha-olefin repeating unit is the polymerized reaction product of ethylene and C3-C12 olefins. For example, the ethylene alpha-olefin repeating unit may comprise ethylene-octene copolymer, ethylenehexene copolymer, ethyl ene-butene copolymer, or a combination thereof.

[0088] In accordance with the present disclosure, the olefin block copolymer may have a melt flow rate (190 °C / 2.16 kg) greater than or equal to about 1 g / 10 min or even greater than or equal to about 5 g / 10 min. The olefin block copolymer may have a melt flow rate (190 °C / 2.16 kg) less than or equal to about 25 g / 10 min or even less than or equal to about 20 g / 10 min. The olefin block copolymer may have a melt flow rate (190 °C / 2.16 kg) from about 1 g / 10 min to about 25 g / 10 min, from about 1 g / 10 min to about 20 g / 10 min, from about 5 g / 10 min to about 25 g / 10 min, or from about 5 g / 10 min to about 20 g / 10 min, or any and all subranges formed from any of these endpoints.

[0089] In accordance with the present disclosure, the olefin block copolymer may have a density greater than or equal to about 0.80 g / cm3or even greater than or equal to about 0.85 g / cm3. The olefin block copolymer may have a density less than or equal to about 0.95 g / cm3or even lessthan or equal to about 0.90 g / cm3. The olefin block copolymer may have a density from about 0.80 g / cm3to about 0.95 g / cm3, from about 0.80 g / cm3to about 0.90 g / cm3, from about 0.85 g / cm3to about 0.95 g / cm3, or from about 0.85 g / cm3to about 0.90 g / cm3, including any and all endpoints and subranges therebetween.

[0090] In accordance with the present disclosure, the olefin block copolymer may have a Shore A hardness greater than or equal to about 50 or even greater than or equal to about 60. The olefin block copolymer may have a Shore A hardness less than or equal to about 85 or even less than or equal to about 75. The olefin block copolymer may have a Shore A hardness from about 50 to about 85, from about 50 to about 75, from about 60 to about 85, or from about 60 to about 75, including any and all endpoints and subranges therebetween.

[0091] Examples of suitable olefin block copolymers that are commercially available include 9500 and 9817 under the INFUSE™ brand from Dow Chemical Company.

[0092] The ethylene alpha-olefin copolymer is the polymerized reaction product of ethylene and C3-C12 olefins. For example, the ethylene alpha-olefin copolymer may comprise ethyleneoctene copolymer, ethyl ene-hexene copolymer, ethyl ene-butene copolymer, or a combination thereof.

[0093] In accordance with the present disclosure, the ethylene-alpha olefin copolymer may have a melt flow rate (190 °C / 2.16 kg) greater than or equal to 0.1 g / 10 min or even greater than or equal to 0.25 g / 10 min. The ethylene-alpha olefin copolymer may have a melt flow rate (190 °C / 2.16 kg) less than or equal to 3 g / 10 min or even less than or equal to 1 g / 10 min. The ethylenealpha olefin copolymer may have a melt flow rate (190 °C / 2.16 kg) from 0.1 g / 10 min to 3 g / 10 min, from 0.1 g / 10 min to 1 g / 10 min, from 0.25 g / 10 min to 3 g / 10 min, or even from 0.25 g / 10 min to 1 g / 10 min, including any and all endpoints and subranges therebetween.

[0094] In accordance with the present disclosure, the ethylene-alpha olefin copolymer may have a density greater than or equal to 0.80 g / cm3or even greater than or equal to 0.85 g / cm3. The ethylene-alpha olefin copolymer may have a density less than or equal to 0.95 g / cm3or even less than or equal to 0.90 g / cm3. The ethylene-alpha olefin copolymer may have a density from 0.80g / cm3to 0.95 g / cm3, from 0.80 g / cm3to 0.90 g / cm3, from 0.85 g / cm3to 0.95 g / cm3, or even from 0.85 g / cm3to 0.90 g / cm3, including any and all endpoints and subranges therebetween.

[0095] In accordance with the present disclosure, the ethylene-alpha olefin copolymer may have a Mooney viscosity (ML 1+4, 121 °C) greater than or equal to 20, greater than or equal to 30, or even greater than or equal to 40. The ethylene-alpha olefin copolymer may have a Mooney viscosity (ML 1+4, 121 °C) less than or equal to 70, less than or equal to 60, or even less than or equal to 50. The ethylene-alpha olefin copolymer may have a Mooney viscosity (ML 1+4, 121 °C) from 20 to 70, from 20 to 60, from 20 to 50, from 30 to 70, from 30 to 60, from 30 to 50, from 40 to 70, from 40 to 60, or from 40 to 50, or any and all subranges formed from any of these endpoints.

[0096] In accordance with the present disclosure, the ethylene-alpha olefin copolymer may have a Shore A hardness greater than or equal to 40 or even greater than or equal to 45. The ethylene-alpha olefin copolymer may have a Shore A hardness less than or equal to 60 or even less than or equal to 65. The ethylene-alpha olefin copolymer may have a Shore A hardness from 40 to 60, from 40 to 55, from 45 to 60, or from 45 to 55, or any and all subranges formed from any of these endpoints.

[0097] Examples of suitable ethylene-alpha olefin copolymers that are commercially available include XLT 8677 under the ENGAGE™ brand from Dow Chemical Company.

[0098] In accordance with the present disclosure, the hot -melt adhesive composition may comprise from about 2 wt.% to about 50 wt.% of the olefin polymer, from about 4 wt.% to about 40 wt.% of the olefin polymer, or from about 6 wt.% to about 30 wt.% of the olefin polymer. The amount of the olefin polymer in the hot-melt adhesive composition may be greater than or equal to about 2 wt.%, greater than or equal to about 4 wt.%, or even greater than or equal to about 6 wt.%. The amount of the olefin polymer in the hot-melt adhesive composition may be less than or equal to about 50 wt.%, less than or equal to about 40 wt.%, less than or equal to about 30 wt.%, less than or equal to about 20 wt.%, less than or equal to about 17 wt.%, less than or equal to about 15 wt.%, less than or equal to about 13 wt.%, or even less than or equal to about 10 wt.%. The amount of olefin polymer in the hot-melt adhesive composition may be from about 2 wt.% to about50 wt.%, from about 2 wt.% to about 40 wt.%, from about 2 wt.% to about 30 wt.%, from about 2 wt.% to about 20 wt.%, from about 2 wt.% to about 17 wt.%, from about 2 wt.% to about 15 wt.%, from about 2 wt.% to about 13 wt.%, from about 2 wt.% to about 10 wt.%, from about 4 wt.% to about 50 wt.%, from about 4 wt.% to about 40 wt.%, from about 4 wt.% to about 30 wt.%, from about 4 wt.% to about 20 wt.%, from about 4 wt.% to about 17 wt.%, from about 4 wt.% to about 15 wt.%, from about 4 wt.% to about 13 wt.%, from about 4 wt.% to about 10 wt.%, from about 6 wt.% to about 50 wt.%, from about 6 wt.% to about 40 wt.%, from about 6 wt.% to about 30 wt.%, from about 6 wt.% to about 20 wt.%, from about 6 wt.% to about 17 wt.%, from about 6 wt.% to about 15 wt.%, from about 6 wt.% to about 13 wt.%, or from about 6 wt.% to about 10 wt.%, or any and all subranges formed from any of these endpoints.Plasticizer

[0099] In accordance with the present disclosure, the hot-melt adhesive composition further comprises a plasticizer. The plasticizer may help to improve flow in the hot-melt adhesive composition. In accordance with the present disclosure, the plasticizer may comprise non-polar plasticizer (e.g., mineral oil). In any of the exemplary aspects, the hot-melt adhesive composition comprises an oil.

[0100] In accordance with the present disclosure, the amount of plasticizer in the hot-melt adhesive composition may be greater than or equal to about 0 wt.%, greater than or equal to about 10 wt.%, greater than or equal to about 20 wt.%, greater than or equal to about 25 wt.%, greater than or equal to about 30 wt.%, or greater than or equal to about 35 wt.%. The amount of plasticizer in the hot-melt adhesive composition may be less than or equal to about 60 wt.%, less than or equal to about 55 wt.%, less than or equal to about 50 wt.%, less than or equal to about 45 wt.%, less than or equal to about 40 wt.%, or less than or equal to about 35 wt.%. The amount of plasticizer in the hot-melt adhesive composition may be from about 0 wt.% to about 60 wt.%, including from about 10 wt.% to 55 wt.%, from about 20 wt.% to 50 wt.%, from about 25 wt.% to 45 wt.%, from about 30 wt.% to 40 wt.%, and any and all subranges formed from any of these endpoints.

[0101] Examples of suitable plasticizers that are commercially available include grade PSO 380 under the PURETOL™ brand from Petro-Canada.Tackifier

[0102] In accordance with the present disclosure, the hot-melt adhesive composition further comprises a tackifier for adhesive applications (e.g., hot-melt adhesive).

[0103] In accordance with the present disclosure, the tackifier may comprise hydrocarbon resin. Exemplary hydrocarbon resins may include aliphatic resins (e.g., C5 resins), aromatic resins (e.g., C9 resins), di cyclopentadiene resins, and resins including a combination of two or more of aliphatic monomers, aromatic monomers, and dicyclopentadiene. The hydrocarbon resin may be hydrogenated. In accordance with the present disclosure, the hydrocarbon resin may have a number average molecular weight of less than or equal to about 2,000 g / mol, less than or equal to about 1,500 g / mol, less than or equal to about 1,200 g / mol, less than or equal to about 1, 100 g / mol, less than or equal to about 1,000 g / mol, or less than or equal to about 900 g / mol.

[0104] In accordance with the present disclosure, the hot-melt adhesive composition may comprise from about 15 wt.% to about 50 wt.% of the tackifier, or from about 17 wt.% to about 40 wt.% of the tackifier, or from about 20 wt.% to about 30 wt.% of the tackifier, based on a total weight of the hot-melt adhesive composition. The amount of tackifier in the hot-melt adhesive composition may be greater than or equal to about 15 wt.%, greater than or equal to about 17 wt.%, or even greater than or equal to about 20 wt.%, based on a total weight of the hot-melt adhesive composition. The amount of tackifier in the hot-melt adhesive composition may be less than or equal to about 50 wt.%, less than or equal to about 40 wt.%, less than or equal to about 30 wt.%, less than or equal to about 27 wt.%, or even less than or equal to about 25 wt.%, based on a total weight of the hot-melt adhesive composition. In any of the aspects disclosed herein, the amount of tackifier in the hot-melt adhesive composition may be from about 15 wt.% to about 50 wt.%, from about 15 wt.% to about 40 wt.%, from about 15 wt.% to about 30 wt.%, from about 15 wt.% to about 27 wt.%, from about 15 wt.% to about 25 wt.%, from about 17 wt.% to about 50 wt.%, from about 17 wt.% to about 40 wt.%, from about 17 wt.% to about 30 wt.%, from about 17 wt.% to about 27 wt.%, from about 17 wt.% to about 25 wt.%, from about 20 wt.% to about 50 wt.%, from about 20 wt.% to about 40 wt.%, from about 20 wt.% to about 30 wt.%, from about 20 wt.% to about 27 wt.%, or even from about 20 wt.% to about 25 wt.%, or any and all endpoints and subranges therebetween.

[0105] Examples of suitable tackifiers that are commercially available include grade R1140 under the PLASTOLYN™ brand from Eastman Chemicals and ESCOREZ™ 5340 (softening point of 140 °C) available from Exxon Mobil Corporation.Co-crosslinkable Polymer

[0106] In accordance with the present disclosure, the hot -melt adhesive composition may further comprise a co-crosslinkable polymer, which may cross-link with the thermoplastic elastomer by the vulcanization package.

[0107] In accordance with the present disclosure, the co-crosslinkable polymer may comprise ethylene-vinyl acetate. The ethylene-vinyl acetate may have a vinyl acetate content greater than or equal to about 10 wt.%, greater than or equal to about 25 wt.%, greater than or equal to about 40 wt.%, or even greater than or equal to 55 wt.%, based on a total weight of the ethylene-vinyl acetate. The ethylene-vinyl acetate may have a vinyl acetate content less than or equal to about 80 wt.%, less than or equal to about 70 wt.%, or even less than or equal to about 60 wt.%. The ethylene-vinyl acetate may have a vinyl acetate content from about 10 wt.% to about 80 wt.%, from about 10 wt.% to about 70 wt.%, from about 10 wt.% to about 60 wt.%, from about 25 wt.% to about 80 wt.%, from about 25 wt.% to about 70 wt.%, from about 25 wt.% to about 60 wt.%, from about 40 wt.% to about 80 wt.%, from about 40 wt.% to about 70 wt.%, from about 40 wt.% to about 60 wt.%, from about 55 wt.% to about 80 wt.%, from about 55 wt.% to about 70 wt.%, or from about 55 wt.% to about 60 wt.%, or any and all endpoints and subranges therebetween.

[0108] In accordance with the present disclosure, the hot-melt adhesive composition may comprise from about 25 wt.% to about 45 wt.% of the co-crosslinkable polymer, or from about 27 wt.% to about 43 wt.% of the co-crosslinkable polymer, or from about 30 wt.% to about 40 wt.% of the co-crosslinkable polymer. The amount of the co-crosslinkable polymer in the hot-melt adhesive composition may be greater than or equal to about 25 wt.%, greater than or equal to about 27 wt.%, or even greater than or equal to about 30 wt.%. The amount of the co-crosslinkable polymer in the hot-melt adhesive composition may be less than or equal to about 45 wt.%, less than or equal to about 43 wt.%, or even less than or equal to about 40 wt.%. The amount of theco-crosslinkable polymer in the hot-melt adhesive composition may be from about 25 wt.% to about 45 wt.%, from about 25 wt.% to about 43 wt.%, from about 25 wt.% to about 40 wt.%, from about 27 wt.% to about 45 wt.%, from about 27 wt.% to about 43 wt.%, from about 27 wt.% to about 40 wt.%, from about 30 wt.% to about 45 wt.%, from about 30 wt.% to about 43 wt.%, or from about 30 wt.% to about 40 wt.%, or any and all endpoints and subranges therebetween.

[0109] Examples of suitable co-vulcanizable polymers that are commercially available include grade 265 under the ELVAX™ brand from Dow Chemical Company.Additives

[0110] In accordance with the present disclosure, the hot-melt adhesive composition may further comprise one or more additives. The additive may comprise adhesion promoters; biocides; anti-fogging agents; anti-static agents; blowing and foaming agents; bonding agents and bonding polymers; dispersants; flame retardants and smoke suppressants; mineral fillers; initiators; lubricants; micas; pigments, colorants, and dyes; processing aids; release agents; silanes, titanates, and zirconates; slip and anti-blocking agents; stearates; ultraviolet light absorbers; viscosity regulators; waxes; or combinations thereof.Crosslinking of Thermoplastic Elastomer

[0111] In accordance with the present disclosure, the hot-melt adhesive composition, including the thermoplastic elastomer, the vulcanization package (e.g., silane), oil, tackifier, the olefin polymer, and any optional components can be blended to form a dynamically vulcanized composition having an advantageous cross-link density and heat resistance.

[0112] In any of the exemplary aspects, the hot-melt adhesive composition may include from 90 to 99.9 parts of the thermoplastic elastomer and 0.1 to 10 parts vulcanization package, including, for example 94 to 99.5 parts thermoplastic elastomer and 0.5 to 5 parts vulcanization package. In any of the exemplary aspects, the hot-melt adhesive composition may comprise the vulcanization package in an amount of 0. 1% to 10%, including, for example, 0.2% to 6%, 0.3% to 4%, 0.5% to 3%, and 1.0% to 2%, based on dry weight of the vulcanization package relative to theweight of the thermoplastic elastomer in the hot-melt adhesive composition, including all endpoints and subranges therebetween.

[0113] The hot-melt adhesive composition can be made by a batch process or a continuous process. Blending (also known as compounding) devices are well known to those skilled in the art and generally include feed means, especially at least one hopper for pulverulent materials and / or at least one injection pump for liquid materials; high-shear blending means, for example a co-rotating or counter-rotating twin-screw extruder, usually comprising a feed screw placed in a heated barrel (or tube); an output head, which gives the extrudate its shape; and means for cooling the extrudate, either by air cooling or by circulation of water. The extrudate is generally in the form of rods continuously exiting the device and able to be cut or formed into granules. However, other forms may be obtained by fitting a die of desired shape on the output die.

[0114] For example, the hot-melt adhesive composition (i.e., the thermoplastic elastomer, the polyolefin polymer, oil, tackifier, the vulcanization package, and any additives) may be fed to an extruder (e.g., 27 MM Leistriz Twin Extruder (L / D 52)) and blended. The blending (e.g., in the barrel of the extruder) may be carried out at a temperature from 240 °F to 450 °F (about 115 °C to about 232 °C). In accordance with the present disclosure, the blending results in carboncarbon bond crosslinking and grafted silane moieties on the thermoplastic elastomer and polyolefin polymer.

[0115] As described herein, the vulcanization package including both organic peroxide and silane enables the carbon-carbon bond crosslinking of the thermoplastic elastomer without the need for additional steps or materials (e.g., moisture cure catalyst). Accordingly, in aspects, the step of blending the thermoplastic elastomer, the organic peroxide, and the silane is performed in the absence of a catalyst. Moreover, the step of blending the thermoplastic elastomer, the organic peroxide, and the silane may be performed in the absence of moisture (e.g., water). Accordingly, the silane may also be grafted to the thermoplastic elastomer in the extruder. However, due to the absence of moisture, silane crosslinking does not occur in the extruder or (to the extent that any crosslinking happens at all) occurs only to a very small degree. However, upon exiting the extruder, the thermoplastic elastomer is free of, or substantially free of, silane-silane cross-links. The extrudate can be applied to a substrate as a hot-melt adhesive. In aspects, the hot-meltadhesive is immersed in hot water to cure the hot-melt adhesive such that the cross-linked polymer system includes silane-silane cross-links.Properties

[0116] In aspects described herein, upon extruding, prior to hot water immersion, the hot- melt adhesive has a tensile elongation at break greater than or equal to about 500% as measured under ASTM D412. For example, the hot-melt adhesive can have a tensile elongation at break of greater than or equal to about 500%, greater than or equal to about 525%, greater than or equal to about 550%, greater than or equal to about 575%, greater than or equal to about 600%, greater than or equal to about 625%, or greater than or equal to about 650%. In aspects of the disclosure, the hot-melt adhesive has a tensile elongation at break of from about 500% to about 800%, from about 550% to about 775%, from about 575% to about 750%, from about 600% to about 725%, or any and all endpoints and subranges therebetween.

[0117] In accordance with the present disclosure, prior to hot water immersion, the hot-melt adhesive may have a Shore A hardness greater than or equal to about 20 as measured under ASTM D2240, including, for example, greater than or equal to about 25, greater than or equal to about 30, greater than or equal to about 35, or greater than or equal to about 40. The hot-melt adhesive may have a Shore A hardness less than about 95, including, for example, less than or equal to about 90, less than or equal to about 85, less than or equal to about 80, less than or equal to about 75, less than about 70, less than about 65, less than about 60, less than about 55, or even less than or equal to about 50. The hot-melt adhesive may have a Shore A hardness from about 20 to about 95, from about 20 to about 90, from about 20 to about 85, from about 20 to about 80, from about 20 to about 75, from about 20 to about 65, from about 20 to about 60, from about 20 to about 55, from about 20 to about 50, from about 25 to about 95, from about 25 to about 90, from about 25 to about 85, from about 25 to about 80, from about 25 to about 75, from about 25 to about 65, from about 25 to about 60, from about 25 to about 55, from about 25 to about 50, from about 30 to about 95, from about 30 to about 90, from about 30 to about 85, from about 30 to about 80, from about 30 to about 75, from about 30 to about 65, from about 30 to about 60, from about 30 to about 55, from about 30 to about 50, from about 35 to about 95, from about 35 to about 90, from about 35 to about 85, from about 35 to about 80, from about 35 to about 75, from about 35 to about 65, fromabout 35 to about 60, from about 35 to about 55, from about 35 to about 50, from about 40 to about 95, from about 40 to about 90, from about 40 to about 85, from about 40 to about 80, from about 40 to about 75, from about 40 to about 65, from about 40 to about 60, from about 40 to about 55, or even from about 40 to about 50, including all endpoints and subranges therebetween.

[0118] In accordance with the present disclosure, prior to hot water immersion, the hot-melt adhesive may have a tensile strength at break greater than or equal to about 1.5 MPa as measured under ASTM D412, greater than or equal to about 2.0 MPa, greater than or equal to about 2.5 MPa, or even greater than or equal to about 3.0 MPa. The hot-melt adhesive may have a tensile strength at break less than or equal to about 8.0 MPa, including, for example, less than or equal to about 7.5 MPa, less than or equal to about 7.0 MPa, less than or equal to about 6.5 MPa, or even less than or equal to about 6.0 MPa. The hot-melt adhesive may have a tensile strength at break from about 1.5 MPa to about 8.0 MPa, from about 1.5 MPa to about 7.5 MPa, from about 1.5 MPa to about 7.0 MPa, from about 1.5 MPa to about 6.5 MPa, from about 1.5 MPa to about 6.0 MPa, from about 2.0 MPa to about 8.0 MPa, from about 2.0 MPa to about 7.5 MPa, from about 2.0 MPa to about 7.0 MPa, from about 2.0 MPa to about 6.5 MPa, from about 2.0 MPa to about 6.0 MPa, from about 2.5 MPa to about 8.0 MPa, from about 2.5 MPa to about 7.5 MPa, from about 2.5 MPa to about 7.0 MPa, from about 2.5 MPa to about 6.5 MPa, from about 2.5 MPa to about 6.0 MPa, from about 3.0 MPa to about 8.0 MPa, from about 3.0 MPa to about 7.5 MPa, from about 3.0 MPa to about 7.0 MPa, from about 3.0 MPa to about 6.5 MPa, or even from about 3.0 MPa to about 6.0 MPa, including all endpoints and subranges therebetween.

[0119] In accordance with the present disclosure, prior to hot water immersion, the hot-melt adhesive can have a Dynamic Mechanical Analysis (DMA) storage modulus at 30 °C and 10 Hz of greater than or equal to about 9 MPa, greater than or equal to about 10 MPa, greater than or equal to about 11 MPa, greater than or equal to about 12 MPa, or greater than or equal to about 13 MPa. For example, the hot-melt adhesive can have a DMA storage modulus at 30 °C and 10 Hz of from about 9 MPa to about 17 MPa, from about 9 MPa to about 16 MPa, from about 9 MPa to about 15 MPa, from about 9 MPa to about 14 MPa, from about 10 MPa to about 17 MPa, from about 10 MPa to about 16 MPa, from about 10 MPa to about 15 MPa, from about 10 MPa to about 14 MPa, from about 11 MPa to about 17 MPa, from about 11 MPa to about 16 MPa, from about11 MPa to about 15 MPa, from about 11 MPa to about 14 MPa, from about 12 MPa to about 17 MPa, from about 12 MPa to about 16 MPa, from about 12 MPa to about 15 MPa, or from about12 MPa to about 14 MPa, including all endpoints and subranges therebetween.

[0120] In accordance with the present disclosure, prior to hot water immersion, the hot-melt adhesive can have a Dynamic Mechanical Analysis (DMA) storage modulus at 80 °C and 10 Hz of greater than or equal to about 4 MPa, greater than or equal to about 4.5 MPa, greater than or equal to about 5 MPa, greater than or equal to about 5.5 MPa, or greater than or equal to about 6 MPa. For example, the hot-melt adhesive can have a DMA storage modulus at 80 °C and 10 Hz of from about 4 MPa to about 10 MPa, from about 4 MPa to about 9 MPa, from about 4 MPa to about 8 MPa, from about 4.5 MPa to about 10 MPa, from about 4.5 MPa to about 9 MPa, from about 4.5 MPa to about 8 MPa, from about 5 MPa to about 10 MPa, from about 5 MPa to about 9 MPa, from about 5 MPa to about 8 MPa, from about 5.5 MPa to about 10 MPa, from about 5.5 MPa to about 9 MPa, or from about 5.5 MPa to about 8 MPa, including all endpoints and subranges therebetween.

[0121] In accordance with the present disclosure, following hot water immersion (80 °C for 24 hours), the cross-linked hot-melt adhesive can have a Dynamic Mechanical Analysis (DMA) storage modulus at 30 °C and 10 Hz of greater than or equal to about 10 MPa, greater than or equal to about 11 MPa, greater than or equal to about 12 MPa, or greater than or equal to about 13 MPa. For example, the cross-linked hot-melt adhesive can have a DMA storage modulus at 30 °C and 10 Hz of from about 10 MPa to about 20 MPa, from about 10 MPa to about 19 MPa, from about 10 MPa to about 18 MPa, from about 10 MPa to about 17 MPa, from about 11 MPa to about 20 MPa, from about 11 MPa to about 19 MPa, from about 11 MPa to about 18 MPa, from about 11 MPa to about 17 MPa, from about 12 MPa to about 20 MPa, from about 12 MPa to about 19 MPa, or from about 12 MPa to about 18 MPa, including all endpoints and subranges therebetween.

[0122] In accordance with the present disclosure, following hot water immersion (80 °C for 24 hours), the cross-linked hot-melt adhesive can have a Dynamic Mechanical Analysis (DMA) storage modulus at 80 °C and 10 Hz of greater than or equal to about 6 MPa, greater than or equal to about 6.5 MPa, greater than or equal to about 7 MPa, greater than or equal to about 7.5 MPa, or greater than or equal to about 8 MPa. For example, the cross-linked hot-melt adhesive can have aDMA storage modulus at 80 °C and 10 Hz of from about 6 MPa to about 12 MPa, from about 6 MPa to about 11.5 MPa, from about 6 MPa to about 11 MPa, from about 6.5 MPa to about 12 MPa, from about 6.5 MPa to about 11.5 MPa, from about 6.5 MPa to about 11 MPa, from about 7 MPa to about 12 MPa, from about 7 MPa to about 11.5 MPa, from about 7 MPa to about 11 MPa, from about 7.5 MPa to about 12 MPa, from about 7.5 MPa to about 11.5 MPa, or from about 7.5 MPa to about 11 MPa, including all endpoints and subranges therebetween.

[0123] In aspects of the present disclosure, the hot-melt adhesive, prior to immersion in hot water, has a fabric bonding peel force of from about 4 Ib / in to about 7 Ib / in, from about 4.5 Ib / in to about 7 Ib / in, from about 5 Ib / in to about 7 Ib / in, from about 4 Ib / in to about 6.5 Ib / in, from about 4.5 Ib / in to about 6.5 Ib / in, from about 5 Ib / in to about 6.5 Ib / in, from about 4 Ib / in to about 6 Ib / in, from about 4.5 Ib / in to about 6 Ib / in, from about 5 Ib / in to about 6 Ib / in, from about 4 Ib / in to about 5.5 Ib / in, from about 4.5 Ib / in to about 5.5 Ib / in, or from about 5 Ib / in to about 5.5 Ib / in, including all endpoints and subranges therebetween.

[0124] In aspects of the present disclosure, the cross-linked hot-melt adhesive, following immersion in hot water (80 °C for 24 hours), has a fabric bonding peel force of from about 4 Ib / in to about 7 Ib / in, from about 4.5 Ib / in to about 7 Ib / in, from about 5 Ib / in to about 7 Ib / in, from about 4 Ib / in to about 6.5 Ib / in, from about 4.5 Ib / in to about 6.5 Ib / in, from about 5 Ib / in to about 6.5 Ib / in, from about 4 Ib / in to about 6 Ib / in, from about 4.5 Ib / in to about 6 Ib / in, from about 5 Ib / in to about 6 Ib / in, from about 4 Ib / in to about 5.5 Ib / in, or from about 4.5 Ib / in to about 5.5 Ib / in, including all endpoints and subranges therebetween.

[0125] In aspects described herein, the cross-linked hot-melt adhesive maintains greater than about 75% of its peel force as measured prior to immersion in hot water. For example, following immersion in hot water (80 °C for 24 hours), the cross-linked hot-melt adhesive maintains greater than about 75% of its peel force, greater than about 80% of its peel force, greater than about 85% of its peel force, or greater than about 90% of its peel force as measured prior to immersion in hot water.Methods of Crosslinking Thermoplastic Elastomers

[0126] In accordance with the present disclosure, the method for forming a cross-linked thermoplastic elastomer comprises blending one or more of the thermoplastic elastomer, the polyolefin polymer, the oil, the tackifier, and the vulcanization package to form a thermoplastic polymer blend. As described above, the vulcanization package may be a dry silane masterbatch, and the thermoplastic elastomer, the polyolefin polymer, and the dry silane masterbatch are dry blended. The method further comprises melting the thermoplastic elastomer and polyolefin polymer to form a cross-linkable thermoplastic polymer melt, and extruding the cross-linkable thermoplastic polymer melt to form a hot-melt adhesive. The method includes a one-step conversion process where the thermoplastic elastomer in the polymer pellet is cross-linked, and there is no separate silane grafting processes.

[0127] As described above, instead of the dry silane masterbatch, the vulcanization package may comprise a solution of the silane crosslinker and the organic peroxide. Accordingly, instead of dry blending the polymers (e.g., the thermoplastic elastomer and the polyolefin polymer) and the dry silane masterbatch and then melting the thermoplastic polymer blend, the method may comprise blending one or more polymers with the solution and melting the blend to form a crosslinkable thermoplastic polymer melt, which is further extruded to form a hot-melt adhesive composition.

[0128] In any aspects described herein, the hot-melt adhesive composition can be prepared as a hot-melt adhesive film or in any other form commonly known and used in hot-melt adhesive applications, including, but not limited to, a sheet, a multi-layer laminate, a coating, a band, a strip, a foam, a tape, a fabric, a filament, a ribbon, a fiber, a plurality of fibers, or a fibrous web.

[0129] In any of the exemplary aspects described herein, the cross-linked hot-melt adhesive composition can be moisture cured by immersion in hot water to further increase storage modulus and significantly improve hot water resistance. In any of the aspects disclosed herein, the hot-melt adhesive may be positioned between substrates to be laminated together and heat and pressure are applied to form the laminate. The laminate is then immersed in direct contact with hot water (e.g., water at a temperature greater than or equal to about 80 °C) to cure the hot-melt adhesive. Accordingly, in any of the aspects described herein, direct water contact, such as contact with hotwater during a washing cycle, is effective to cure the hot-melt adhesive without the use of a catalyst.Applications

[0130] As described above, the hot-melt adhesive composition may be prepared in any form, such as an adhesive film or an adhesive webbing. In aspects in which the hot-melt adhesive composition is prepared as an adhesive film, the film has a thickness of from about 15 pm to about 300 pm, from about 18 pm to about 100 pm, or from about 20 pm to about 55 pm. The film can have a width of from about 5 cm to about 40 cm.

[0131] In any of the aspects, the hot-melt adhesive composition (e.g., the adhesive film, adhesive web, etc.) can be incorporated into a multilayer composite. The multilayer composite can include two or more films or layers. According to aspects described herein, the multilayer composite can include the adhesive film adhered to a fabric backing (e.g., substrate). In one or more aspects described herein, the multilayer composite can include the adhesive film adhered to a release liner.

[0132] In any of the aspects disclosed herein, the hot-melt adhesive composition may be used in textile or garment applications. In such applications, substrates to which the hot-melt adhesive composition is adhered to can include various fabrics and textiles, including but not limited to, nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, elastane, and combinations thereof. According to aspects provided herein, the hot-melt adhesive composition is used to form an adhesive layer in a seam. The adhesive layer can be, for example, an adhesive film or adhesive webbing. The seam can include a first section of fabric, a second section of fabric, and the adhesive layer. The fabric of the first section and the fabric of the second section can be the same type of fabric (e.g., nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, elastane, and combinations thereof) or different types of fabric. The second section of fabric at least partially overlaps the first section of fabric to form a seam section. The adhesive layer is disposed in the seam section and adheres the first section of fabric to the second section of fabric.

[0133] A seam is prepared by supplying a first section of fabric, a second section of fabric, and an adhesive layer according to any of the aspects described herein. As described above, the fabric of the first section and the fabric of the second section can be the same type of fabric (e.g., nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, elastane, and combinations thereof) or different types of fabric. The adhesive layer is situated between the first section of fabric and the second section of fabric to form a seam section, with the second section of fabric at least partially overlapping the first section of fabric. The seam section can be stitchless (e.g., does not include stitches attaching the first section of fabric to the second section of fabric) or can include stitches attaching the first section of fabric to the second section of fabric. The seam section is then heated such that the adhesive layer adheres the first section of fabric and the second section of fabric.EXAMPLES

[0134] Table 1 below illustrates sources of ingredients used to form Comparative ExamplesC1-C2 and Examples E1-E5.

[0135] Table 1:

[0136] Tables 2-3 below illustrate the formulations used to form and certain properties of Comparative Examples C1-C2 and Examples E1-E5.

[0137] To prepare samples for Comparative Examples C1-C2 and Examples E1-E5, the components of the formulations listed in Tables 2-3 were added into a 27 MM Leistriz Twin Extruder (L / D / 52) and blended at a barrel temperature of 194 °C and a rate of 400 rotations per minute. The mixed formulation was extruded at a speed of from about 6.30 g / s to about 7.6 g / s at 194 °C using a die having a width of 6 inches (approximately 15.2 cm).

[0138] Laminated films were prepared by placing the film between two layers of fabric. The fabric was a nylon / spandex fabric. Lamination was performed by heating the layers to a temperature of 160 °C for 30 seconds.

[0139] Temperature resistance is reported as the Dynamic Mechanical Analysis (DMA) storage modulus, measured using a Q800 DMA where samples were heated from 30 °C to 100 °C at a rate of 3 °C / minute with an oscillation frequency of 10 Hz. For samples immersed in water, following water immersion, the laminate was dried at room temperature for 24 hours before peeling test was conducted. Peel force was measured using an Instron at a peel angle of 180 °. Shore A hardness, modulus at 100%, tensile strength at break, and tensile elongation at break were tested prior to water immersion.Table 2*Fails at 55 °C

[0140] Table 3

[0141] As shown in Table 2, Comparative Examples Cl and C2 used standard, fully hydrogenated SEBS with a low molecular weight (Comparative Example Cl) or a high molecular weight (Comparative Example C2). The comparative examples were not cross-linked as describedherein. Comparative Example Cl exhibited good think film extrusion at a 1-2 mil thickness, but the DMA storage modulus could only be measured to 55 °C before the film lost its rigidity and could not be evaluated further. Additionally, Comparative Example Cl lost more than 40% of its peel force after water immersion. Comparative Example C2 included a fully hydrogenated SEBS having a higher molecular weight than the SEBS of Comparative Example C2. As a result of the increased molecular weight, Comparative Example C2 could not be extruded into a thin film. The DMA storage modulus at 80 °C of Comparative Example C2 (7 MPa) is comparable to the DMA storage modulus at 30 °C of Comparative Example Cl (7MPa), indicating that the higher molecular weight SEBS exhibits improved temperature resistance than the low molecular weight hydrogenated SEBS.

[0142] As shown in Table 3, cross-linked polymer systems formed from a dynamically vulcanizable composition including a thermoplastic elastomer in the form of a partially hydrogenated SEBS (p-SEBS), a polyolefin polymer (FORMOLENE® 1102K or INFUSE™ D9500), an oil (PURETOL™ PSO 380), a tackifier (ESCOREZ™ 5340), silane (SILQUEST™ A- 171), and organic peroxide (PERKADOX® BC-FF) (Examples E1-E4) formed good thin films while exhibiting improved hot water resistance. Example E3 is similar in formulation to Examples El and E2, but further included EPDM rubber. Example E4 includes EPDM rubber and an olefin block copolymer (INFUSE™ D9500) in place of the polypropylene (FORMOLENE® 1102K) used in Examples E1-E3. The DMA storage modulus of Examples El and E3 at 80 °C was higher than DMA storage modulus of Comparative Example C2 at 80 °C, and further increased following immersion in hot water. Moreover, Examples E1-E4 maintained more than 90% of their peel force following hot water immersion. Example E3 exhibited no loss of peel strength following hot water immersion. Examples E3 and E4 demonstrate that various polyolefin polymers can be incorporated without adversely impacting the processability or hot water resistance. Additionally, Examples E3 and E4 demonstrate that the incorporation of EPDM can further increase the hot water resistance without adversely impacting the processability.

[0143] Example E5 in Table 3 shows that cross-linked polymer systems formed from a dynamically vulcanizable composition including a thermoplastic elastomer in the form of a fully hydrogenated SEBS (KRATON™ G1650), EPDM rubber, a polyolefin polymer(FORMOLENE® 1102K), an oil (PURETOL™ PSO 380), a tackifier (ESCOREZ™ 5340), silane (SILQUEST™ A-171), and organic peroxide (PERKADOX® BC-FF) form good thin films while exhibiting improved hot water resistance. In particular, Example E5 includes the same SEBS polymer as Comparative Example Cl (KRATON™ G1650), but the incorporation of the EPDM and crosslinking provides an improved DMA modulus at 80 °C. Although the DMA modulus at 80 °C of Example E5 is initially lower than the DMA modulus at 80 °C of Comparative Example C2, following hot water immersion, the DMA modulus at 80 °C of Example E5 is greater than that of Comparative Example C2. Moreover, following 24 hours immersion in hot water, Example E5 maintains greater than 90% of its peel force.

[0144] Accordingly, Examples E1-E5 demonstrate that moisture curing increases the DMA modulus at 80 °C above that of Comparative Example E2, which includes a high molecular weight SEBS, while enabling the composition of Examples E1-E5 to be extruded into thin films. Each of Examples E1-E5 also demonstrates significant improvement in hot water resistance.

[0145] It will be apparent that modifications and variations are possible without departing from the scope of the disclosure defined in the appended claims. More specifically, although some aspects of the present disclosure are identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to these aspects.

Claims

CLAIMS1. A hot-melt adhesive composition comprising, a dynamically vulcanized composition comprising the reaction product of: a cross-linkable thermoplastic elastomer comprising: a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene terpolymer; or a fully hydrogenated conjugated diene-vinyl aromatic copolymer and ethylene propylene diene terpolymer; a polyolefin polymer; oil; a tackifier; and a silane compound.

2. The hot-melt adhesive composition of any of the preceding claims, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer is selected from the group consisting of partially hydrogenated styrene-butadiene rubber, partially hydrogenated styrene-butadiene block copolymers, partially hydrogenated styrene-isoprene block copolymers, partially hydrogenated styrene-butadiene-isoprene rubber, partially hydrogenated styrene-butadiene / isoprene block copolymers, partially hydrogenated styrene-butadiene-isoprene block copolymers, and combinations thereof.

3. The hot-melt adhesive composition of any of the preceding claims, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer a block copolymer that includes a block defined by formula (I):wherein the w, x, y, and z units are randomly distributed in the block, each Ri is independently a hydrogen atom or a methyl group, each R2 is independently a hydrogen atom or a methyl groupwith the proviso that at least one R2 per unit is a hydrogen atom; and the molar percent of the sum of the y and z units out of the total sum of the w, x, y, and z units in the block is from about 30% to about 90%.

4. The hot-melt adhesive composition of any of the preceding claims, wherein the partially unsaturated conjugated diene-vinyl aromatic copolymer has a number average molecular weight from about 50,000 g / mol to about 200,000 g / mol.

5. The hot-melt adhesive composition of any of the preceding claims, wherein the fully hydrogenated conjugated diene-vinyl aromatic copolymer has a number average molecular weight from about 50,000 g / mol to about 200,000 g / mol.

6. A hot-melt adhesive webbing comprising the adhesive composition of any of the previous claims.

7. A hot-melt adhesive fdm comprising the adhesive composition of any of claims 1-6.

8. The hot-melt adhesive film of claim 7, wherein the adhesive film has a thickness of 20 pm to 300 pm.

9. The hot-melt adhesive film of claim 8, wherein the adhesive film is part of a multilayer composite comprising two or more films.

10. The hot-melt adhesive film of any of claims 7-9, wherein the adhesive film is part of a multilayer composite comprising the film adhered to a fabric backing.

11. The hot-melt adhesive film of any of claims 7-9, wherein the adhesive film is part of a multilayer composite comprising the film adhered to a release liner.

12. The hot-melt adhesive film of any of claims 7-9, wherein the adhesive film has a width of 5 cm to 40 cm.

13. A seam compri si ng : a first section of fabric;a second section of fabric at least partially overlapping the first section of fabric to form a seam section; and a hot-melt adhesive layer in the seam section adhering the first section of fabric to the second section of fabric, wherein the adhesive layer comprises an adhesive film or an adhesive webbing comprising the hot-melt adhesive composition of any of claims 1-5.

14. The seam of claim 13, wherein the seam section includes stitches attaching the first section of fabric to the second section of fabric.

15. The seam of claim 13 or claim 14, wherein the seam section is a stitchless seam section.

16. The seam of any of claims 13-15, wherein the first section of fabric and the second section of fabric each comprise nylon, polyester, acrylic, polyurethane, olefin, neoprene, acetate, elastane, or a combination thereof.

17. The seam of any of claims 13-16, wherein the adhesive layer is the adhesive film.

18. The seam of any of claims 13-16, wherein the adhesive layer is the adhesive webbing.

19. A method of preparing a seam comprising: supplying a first section of fabric, a second section of fabric, and a hot-melt adhesive layer; situating the hot-melt adhesive layer between the first section of fabric and the second section of fabric to form a seam section, wherein the second section of fabric at least partially overlaps the first section of fabric; and heating the seam section such that the adhesive layer adheres the first section of fabric and the second section of fabric, wherein the hot-melt adhesive layer compromises an adhesive composition comprising a dynamically vulcanized composition comprising the reaction product of thermoplastic elastomer comprising: a cross-linkable polymer composition comprising: a partially unsaturated conjugated diene-vinyl aromatic copolymer and optionally ethylene propylene diene terpolymer; ora fully hydrogenated conjugated diene-vinyl aromatic copolymer and ethylene propylene diene terpolymer; a polyolefin polymer; oil; a tackifier; and a silane compound.

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